title: Hydroalkoxylation of unactivated olefins with carbon radicals and carbocation species as key intermediates.
abstract: A unique Markovnikov hydroalkoxylation of unactivated olefins with a cobalt complex, silane, and N-fluoropyridinium salt is reported. Further optimization of reaction conditions yielded high functional group tolerance and versatility of alcoholic solvent employed, including methanol, i-propanol, and t-butanol. Use of trifluorotoluene as a solvent made the use of alcohol in stoichiometric amount possible. Mechanistic insight into this novel catalytic system is also discussed. Experimental results suggest that catalysis involves both carbon radical and carbocation intermediates.
authors.affiliation: Faculty of Pharmacy, Musashino University, 1-1-20 Shinmachi Nishitokyo-shi, Tokyo 202-8585, Japan. cgehisa@musashino-u.ac.jp
authors.forename: Hiroki
authors.initials: H
authors.lastname: Shigehisa
authors.forename: Tatsuya
authors.initials: T
authors.lastname: Aoki
authors.forename: Sumiko
authors.initials: S
authors.lastname: Yamaguchi
authors.forename: Nao
authors.initials: N
authors.lastname: Shimizu
authors.forename: Kou
authors.initials: K
authors.lastname: Hiroya
mesh_terms: D000438:Alcohols / Q000138:chemical synthesis* / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D003035:Cobalt / Q000737:chemistry; D005609:Free Radicals / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry; D011726:Pyridinium Compounds / Q000737:chemistry; D012821:Silanes / Q000737:chemistry
chemical_list: D000438:Alcohols; D000475:Alkenes; D005609:Free Radicals; D009942:Organometallic Compounds; D011726:Pyridinium Compounds; D012821:Silanes; D003035:Cobalt; D002244:Carbon